Hydrocarbon conversion catalysts

ABSTRACT

Composition of matter suitable as a catalyst (base) in hydroprocessing comprising a crystalline aluminosilicate zeolite and a binder wherein the crystalline aluminosilicate comprises a modified Y zeolite having a unit cell size below 24.35 Å, a degree of crystallinity which is at least retained at increasing SiO 2  /Al 2  O 3  molar ratios, a water adsorption capacity (at 25° C. and a p/p o  value of 0.2) of at least 8% by weight of modified zeolite and a pore volume of at least 0.25 ml/g wherein between 10% and 60% of the total pore volume is made up of pores having a diameter of at least 8 nm. The invention also relates to hydroconversion catalysts and processes based on said compositions of matter.

This is a division of application Ser. No. 055,652, filed May 29, 1987,now U.S. Pat. No. 4,857,170.

FIELD OF THE INVENTION

The present invention relates to hydrocarbon conversion processes andcatalysts which can be used in such processes. The present inventionalso relates to compositions of matter suitable as catalyst or catalystbase in hydroprocessing, particularly in hydrocracking.

BACKGROUND OF THE INVENTION

Of the many hydroconversion processes known in the art, hydrocracking isbecoming increasingly important since it offers product flexibilitytogether with product quality. As it is also possible to subject ratherheavy feedstocks to hydrocracking it will be clear that much attentionhas been devoted to the development of hydrocracking catalysts.

Modern hydrocracking catalysts are generally based on zeolitic materialswhich may have been adapted by techniques like ammonium ion exchange andvarious forms of calcination in order to improve the performance of thehydrocracking catalysts based on such zeolites.

One of the zeolites which is considered to be a good starting materialfor the manufacture of hydrocracking catalysts is the well-knownsynthetic zeolite Y as described in U.S. Pat. No. 3,130,007 issued Apr.21, 1964. A number of modifications has been reported for this materialwhich include, inter alia, ultrastable Y (U.S. Pat. No. 3,536,605 issuedOct. 27, 1970) and ultrahydrophobic Y (U.K. Patent ApplicationGB-A-2,014,970, published Sept. 5, 1979). In general, it can be saidthat the modifications cause a reduction in the unit cell size dependingon the treatment carried out.

The ultrahydrophobic zeolites as described in GB-A-2,014,970 are alsoreferred to in European Patent Application EP-B-28,938 published May 20,1981, and European Patent Specification EP-B-70,824 published Feb. 5,1986 as suitable components for hydrocracking catalysts. From saidpublications it appears that such zeolites have an intrinsically lowwater adsorption capacity. Water adsorption capacities below 5%(EP-B-28,938), respectively 8% (EP-B-70,824) by weight of zeolite areconsidered to be the maximum levels acceptable and it is confirmedexperimentally in EP-B-28,938 that a water adsorption capacity of 8.5%by weight on zeolite causes a drastic decrease in selectivity.

In European Patent Application EP-A-162,733 published Nov. 11, 1985,zeolite Y components for hydrocracking catalysts are described whichmust possess a rather stringent pore diameter distribution which inessence means that at least 80% of the total pore volume is made up ofpores having a diameter of less than 2 nm, and preferably at least 85%of the total pore volume is made up of pores having a diameter of lessthan 2 nm.

In U.K. Patent Application GB-A-2,114,594 published Aug. 24, 1983, aprocess for the production of middle distillates is disclosed whereinuse is made of catalysts comprising so-called expanded pore faujasiticzeolites. The pore expansion referred to in said patent specificationhas been obtained by firstly steaming the faujasitic zeolite at atemperature of at least 538° C., in particular at a temperature above760° C., followed by contacting the steamed faujasitic zeolite with anacid, preferably an acid having a pH less than 2. It should be notedthat the degree of crystallinity retained in the expanded pore zeolitedramatically decreases at increasing amounts of acid used (see FIG. 3 ofGB-A-2,114,594). Since the SiO₂ /Al₂ O₃ molar ratio substantiallyincrease linearly with the amounts of acid used (see FIG. 2) it appearsthat the crystallinity of the faujasitic zeolites treated according tothe process described in GB-A-2,114,594 intrinsically decreases atincreasing SiO₂ /Al₂ O₃ molar ratios.

It has now been found that the use of certain modified Y zeolites ascomponents in hydrocracking catalysts gives an unexpected highselectivity to the desired product(s) combined with a significantlylower gas make than experienced thus far with catalysts based on Yzeolite. Moreover, it was found that the quality of the product(s) wasimproved despite a lower hydrogen consumption. These improvements areeven more remarkable since they can be achieved with catalysts showing ahigher activity than thus far achievable with Y type zeolites.

SUMMARY OF THE INVENTION

The present invention relates to compositions of matter suitable as acatalyst (base) in hydroprocessing comprising a crystallinealuminosilicate zeolite and a binder wherein the crystallinealuminosilicate comprises a modified Y zeolite having a unit cell sizebelow 24.35 Å, a degree of crystallinity which is at least retained atincreasing SiO₂ /Al₂ O₃ molar ratios, a water adsorption capacity (at25° C. and a p/p_(o) value of 0.2) of at least 8% by weight of modifiedzeolite and a pore volume of at least 0.25 ml/g wherein between 10% and60% of the total pore volume is made up of pores having a diameter of atleast 8 nm.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preference is given to compositions of matter wherein between 10% and40% of the total pore volume of the modified Y zeolite is made up ofpores having a diameter of at least 8 nm. The pore diameter distributionis determined by the method described by E. P. Barrett, G. Joyner and P.P. Halenda (J. Am. Chem. Soc. 73, 373 (1951)) and is based on thenumerical analysis of the nitrogen desorption isotherm. It should benoted that inter-crystalline voids are excluded in the determination ofthe percentage of the total pore volume made up in pores having adiameter of at least 8 nm when said percentage is between 10% and 40%.

It has been found that very good results in terms of performance andactivity can be obtained when modified Y zeolites are used having awater adsorption capacity of at least 10% by weight on zeolite, inparticular between 10% and 15% by weight of zeolite. The wateradsorption capacity of the modified Y zeolites present in thecompositions of matter and/or the catalysts according to the presentinvention is measured at 25° C. and a p/p_(o) value of 0.2. In order todetermine the water adsorption capacity the modified Y zeolite isevacuated at elevated temperature, suitably 400° C., and subsequentlysubjected at 25° C. to a water pressure corresponding to a p/p_(o) valueof 0.2 (ratio of the partial water pressure in the apparatus and thesaturation pressure of water at 25° C.).

The unit cell size of the modified Y zeolites present in thecompositions of matter is below 24.35 Å (as determined by ASTM-D-3492,the zeolite being present in its NH₄ ⁺ -form). It should be noted thatthe unit cell size is but one of the parameters which determine thesuitability of modified Y zeolites. It has been found that also thewater adsorption capacity and the pore diameter distribution as well asthe crystallinity have to be taken into account in order to be able toobtain marked improvements in performance as referred to hereinbefore.

As regards crystallinity it should be noted that the modified Y zeolitesaccording to the present invention should at least retain theircrystallinity (relative to a certain standard, e.g., Na-Y) whencomprising crystallinity as a function of increasing SiO₂ /Al₂ O ₃ molarratio. Generally, the crystallinity will slightly improve when comparingmodified Y zeolites with increasing SiO₂ /Al₂ O₃ molar ratios.

The compositions of matter according to the present invention suitablycomprise 5-90% by weight of modified Y zeolite and 10-95% by weight ofbinder. Preferably the compositions of matter comprise rather highamounts of modified Y zeolite: 50-85% by weight of modified Y zeoliteand 15-50% by weight of binder being particularly preferred.

The binder(s) present in the composition(s) of matter suitably compriseinorganic oxides or mixtures of inorganic oxides. Both amorphous andcrystalline binders can be applied. Examples of suitable binderscomprise silica, alumina, silica-alumina, clays, zirconia,silica-zirconia and silica-boria. Preference is given to the use ofalumina as binder.

Depending on the desired unit cell size the SiO₂ /Al₂ O₃ molar ratio ofthe modified Y zeolite will have to be adjusted. There are manytechniques described in the art which can be applied to adjust the unitcell size accordingly. It has been found that modified Y zeolites havinga SiO₂ /Al₂ O₃ molar ratio between 4 and 25 can be suitably applied asthe zeolitic component of the compositions of matter according to thepresent invention. Preference is given to modified Y zeolites having amolar SiO₂ /Al₂ O₃ ratio between 8 and 15.

The present invention further relates to catalyst compositionscomprising besides a binder and modified Y zeolite as definedhereinbefore at least one hydrogenation component of a Group VI metaland/or at least one hydrogenation component of a Group VIII metal.Suitably, the catalyst compositions according to the present inventioncomprise one or more components of nickel and/or cobalt and one or morecomponents of molybdenum and/or tungsten or one or more components ofplatinum and/or palladium.

The amount(s) of hydrogenation component(s) in the catalyst compositionssuitably range between 0.05 and 10% by weight of Group VIII metalcomponent(s) and between 2 and 40% by weight of Group VI metalcomponent(s), calculated as metal(s) per 100 parts by weight of totalcatalyst. The hydrogenation components in the catalyst compositons maybe in the oxidic and/or the sulphidic form. If a combination of at leasta Group VI and a Group VIII metal component is present as (mixed)oxides, it will be subjected to a sulphiding treatment prior to properuse in hydrocracking.

The present invention also relates to a process for convertinghydrocarbon oils into products of lower average molecular weight andlower average boiling point wherein a hydrocarbon oil is contacted atelevated temperature and pressure in the presence of hydrogen with acatalyst comprising a modified Y zeolite having a unit cell size below24.35 Å, a water adsorption capacity (at 25° C. and a p/p_(o) value of0.2) of at least 8% by weight of modified zeolite and a pore volume ofat least 0.25 ml/g wherein between 10% and 60% of the total pore volumeis made up of pores having a diameter of at least 8 nm, a binder and atleast on hydrogenation component of a group VI metal and/or at least onehydrogenation component of a Group VIII metal.

Preferably, the hydroconversion process is carried out by usingcatalysts comprising a modified Y zeolite wherein between 10% and 40% ofthe total pore volume (excluding inter-crystalline voids) is made up ofpores having a diameter of at least 8 nm. Good results have beenobtained using modified Y zeolites in the catalyst compositions whereinthe water adsorption capacity is at least 10% by weight of modifiedzeolite, and in particular between 10% and 15% by weight of modifiedzeolite.

Suitably, the process according to the present invention is carried outusing a catalyst composition comprising 5-90% by weight of modified Yzeolite and 10-95% by weight of binder, and preferably 50-85% by weightof modified Y zeolite and 15-50% by weight of binder. Suitable binderscomprise inorganic oxides or mixtures of inorganic oxides. Examples ofbinders comprise silica, alumina, silica-alumina, clay, silica-zirconiaand silica-boria. Preference is given to the use of alumina as binder.

Modified Y zeolites having a SiO₂ /Al₂ O₃ molar ratio between 4 and 25and in particular between 8 and 15 can be suitably applied as thezeolitic components in the catalyst compositions to be used in thehydroconversion process according to the present invention.

Preferably, the process according to the present invention is carriedout by using catalysts comprising, in addition to the zeolitic componentand the binder, one or more components of nickel and/or cobalt and oneor more components of molybdenum and/or tungsten or one or morecomponents of platinum and/or palladium. In particular, use is made ofhydrogenation components comprising between 0.05 and 10% by weight ofnickel and between 2and 40% by weight of tungsten, calculated as metalsper 100 parts by weight of total catalyst. Preferably the hydrogenationcomponents are used in sulphided form.

Hydroconversion process configurations in accordance with the presentinvention are those wherein a substantial reduction in average molecularweight and boiling point can be accomplished by contacting the feed witha catalyst composition comprising a modified Y zeolite as describedhereinbefore and a binder.

Examples of such processes comprise single-stage hydrocracking,two-stage hydrocracking, series-flow hydrocracking as well as mildhydrocracking.

It will be appreciated that the hydroconversion processes in accordancewith the present invention can also be carried out suitably inbunker-type operations, i.e., by using reactor vessels allowing forperiodical or intermittent catalyst removal and replenishment. Use canbe made of the various bunker-techniques described in the art.

Feedstocks which can be suitably applied in the process according to thepresent invention comprise gas oil, vacuum gas oils, deasphalted oils,long residues, catalytically cracked cycle oils, coker gas oils andother thermally cracked gas oils and syncrudes, optionally originatingfrom tar sands, shale oils, residue upgrading processes or biomass.Combinations of various feedstocks can also be applied.

It may be desirable to subject part or all of the feedstock to one ormore (hydro)treatment steps prior to its use in the hydrocarbonconversion process according to the present invention. It is often foundconvenient to subject the feedstock to a (partial) hydrotreatment. Whenrather heavy feedstocks are to be processed it will be advantageous tosubject such feedstocks to a (hydro) demetallization treatment.

Suitable process conditions to be applied comprise temperatures in therange of from 250° C. to 500° C., pressures up to 300 bar and spacevelocities between 0.1 and 10 kg feed per liter of catalyst per hour(kg/l/h). Gas/feed ratios between 100 and 5000 Nl/kg feed (normal litersat standard temperature and pressure per kilogram) can suitably be used.

Preferably, the hydroconversion process according to the presentinvention is carried out at a temperature between 300° C. and 450° C., apressure between 25 and 200 bar and a space velocity between 0.2 and 5kg feed per liter of catalyst per hour. Preferably, gas/feed ratiosbetween 250 and 2000 are applied.

The catalysts to be used in the hydrocarbon conversion process accordingto the present invention, and in particular in the hydrocracking processappear to be very flexible as they are capable of producing productfractions with narrow boiling point ranges because of their inherentproperty of limited overcracking. Therefore, they can be usedadvantageously in various modes of operation dependent on the desiredproduct slate.

It is thus possible to use as feed a hydrocarbon oil fraction having aboiling point range slightly above the boiling point range of theproduct to be obtained in the process. However, substantially higherboiling feeds can also be used conveniently to produce materials ofsimilar product boiling point range. For instance, a vacuum gas oilappears to be an excellent feedstock to produce middle distillates usingthe catalysts in accordance with the present invention but also naphthacan be produced in high yields. By adjusting, for instance, theoperating temperature and/or the recycle cut-point (when operating inrecycle mode) either middle distillate or naphtha will become the mainproduct while retaining high selectivity with respect to the desiredproduct.

The ranges and limitations provided in the instant specification andclaims are those which are believed to particularly point out anddistinctly claim the instant invention. It is, however, understood thatother ranges and limitations that perform substantially the samefunction in substantially the same manner to obtain the same orsubstantially the same result are intended to be within the scope of theinstant invention as defined by the instant specification and claims.

The present invention will now be illustrated by means of the followingexamples which are provided for illustration and are not to be construedas limiting the invention.

Example I

(a) Preparation of modified Y zeolite/binder composition

A commercially available ammonium-ultra stable zeolite Y having a unitcell size of 24.57 Å, a sodium oxide content of 0.21% wt and a SiO₂ /Al₂O₃ molar ratio of about 6 was subjected to an ion-exchange treatmentwith 0.2M aluminum sulphate for one hour under reflux-conditions.Thereafter, the material thus treated was subjected to a calcination inthe presence of steam for a period of one hour at 700° C. The calcinedmaterial obtained had a unit cell size of 24.30 Å and a SiO₂ /Al₂ O₃molar ratio of 6.85.

The material obtained was then subjected to an ion-exchange treatmentwith 0.16M aluminum sulphate for one hour under reflux conditionsfollowed by a treatment with 1M ammonium nitrate under the sameconditions. This latter treatment was repeated once. The modifiedY-zeolite obtained had a unit cell size of 24.33 Å and a SiO₂ /Al₂ O₃molar ratio of 9.85.

466 Grams of said modified Y zeolite having a unit cell size of 24.33 Å,a SiO₂ /Al₂ O₃ molar ratio of 9.85, a water adsorption capacity (at 25°C. and a p/p_(o) value of 0.2) of 11.3% by weight, a nitrogen porevolume of 0.40 ml/g wherein 18% of the total pore volume is made up ofpores having a diameter>8 nm and a loss of ignition (550° C.) of 14.1%by weight is mixed with 135 g hydrated aluminum oxide (boehmite, exCondea) with a loss on ignition of 25.8% by weight. Subsequently asolution of 5 g of acetic acid and 302.6 g of water was added to thepowdery mixture. After mulling the mixture obtained it was extruded in aBonnot extruder provided with a die plate producing 1.5 mm extrudates.The extrudates obtained were dried for 2 hours at 120° C. and finallycalcined for 2 hours at 500° C. The extrudates obtained had a water porevolume of 0.66 ml/g.

(b) Preparation of catalyst composition

50 Grams of the extrudates as prepared according to the proceduredescribed in Example Ia were dried at 450° C. for 1 hour prior toimpregnation with 33 ml of a solution which is made up of 25 g of asolution prepared by blending 214.3 g of a nickel nitrate solution (14%by weight of Ni), 150 g of water and 137 g of ammonium meta tungstate(69.5% by weight of W), and 8 g of water. The impregnated extrudes werehomogenized for 1 hour using a rolling device. Finally themetal-containing extrudates were dried for 2 hours at 120° C. andcalcined at 500° C. for 1 hour. The catalyst obtained contained 2.6% byweight of nickel and 8.2% by weight of tungsten. The ready catalystcontained 77.5% by weight of modified Y zeolite and 22.5% by weight ofbinder (based on total amount of zeolite and binder on a dry basis).

(c) Hydrocracking experiments

The catalyst was described in Example Ib was subjected to ahydrocracking performance test involving a low sulphur, low nitrogenvacuum gas oil having the following properties:

    ______________________________________                                        C (% wt)         86.2                                                         H (% wt)         13.8                                                         d (70/4)          0.826                                                       viscosity (100° C.)                                                                      4.87 cS (ASTM-D-445)                                        viscosity (60° C.)                                                                      12.43 cS (ASTM-D-445)                                        RCT (% wt)        0.05 (ASTM-D-542)                                           I.B.P.           205° C.                                               10/20            332/370                                                      30/40            392/410                                                      50/60            428/448                                                      70/80            467/492                                                      90               525                                                          F.B.P.           598                                                          ______________________________________                                    

The catalyst was firstly subjected to a presulphiding treatment byslowly heating in a 10% v H₂ S/H₂ -atmosphere to a temperature of 370°C. The catalyst was tested in a 1:1 dilution with 0.2 mm SiC particlesunder the following operating conditions: WHSV 1.1 kg.l¹.h⁻¹, H₂ Spartial pressure 1.4 bar, total pressure 130 bar and a gas/feed ratio of1,000 Nlkg⁻¹. The experiment was carried out in once-through operation.When operating the hydrocracking in a kerosene mode of operation, thecatalyst performance is expressed at 70% by weight conversion of 300°C.⁺ boiling point material in the feed after allowing the catalyst tostabilize.

The following results were obtained:

Temperature required (70% conv. 300° C.⁺): 318° C.

Distribution of 300° C.⁻ product (in a % by weight)

    ______________________________________                                               C.sub.1 --C.sub.4                                                                              7                                                            C.sub.5 - 130° C.                                                                      46                                                            130° C.-300° C.                                                                 47                                                     ______________________________________                                    

The chemical hydrogen consumption amount to 1.2% by weight.

Example II

The hydrocracking experiment as described in Example Ic was repeated inthe naphtha mode of operation, i.e., the catalyst as described inExample Ib was subjected to the presulphiding, the feedstock andoperating conditions as described in Example Ic but in this case theperformance is expressed at 70% by weight conversion of 180° C.⁺ boilingpoint material in the feed.

The following results were obained:

Temperature required (70% conv. of 180° C.⁺): 321° C.

Distribution of 180° C.⁻ product (in % by weight):

    ______________________________________                                               C.sub.1 --C.sub.4                                                                             11                                                            C.sub.5 - 65° C.                                                                       21                                                            65° C.-180° C.                                                                  68                                                     ______________________________________                                    

The chemical hydrogen consumption amounted to 1.3% by weight.

Comparative Example

A commercially available ultra-stable Y zeolite having a unit cell sizeof 24.56 Å, a water absorption capacity of 24% by weight (at 25° C. anda p/p_(o) value of 0.2) and a nitrogen pore volume of 0.38 ml/g wherein8% of the total pore volume is made up of pores having a diameter of >8nm was treated with hydrated aluminum oxide and a solution of nickelnitrate and ammonium metatungstate so as to obtain a catalyst containing2.6% by weight of nickel and 8.2% by weight of tungsten.

The comparative catalyst was subjected to a presulphiding treatment asdescribed in Example Ic and subjected to the same feed. When operatingin kerosene mode (i.e. expressing catalyst performance at 70% by weightconversion of 300° C.⁺ boiling point material in the feed) afterallowing the catalyst to stabilize, the following results were obtained:

Temperature requirement (70% conv. of 300° C.⁺): 325° C.

Distribution of 300° C.⁻ product (in % by weight):

    ______________________________________                                               C.sub.1 --C.sub.4                                                                             13                                                            C.sub.5 - 130° C.                                                                      57                                                            130° C.-300° C.                                                                 30                                                     ______________________________________                                    

The chemical hydrogen consumption amounted to 1.5% by weight.

The comparative catalyst was also subjected to an experiment asdescribed in Example II, i.e., in the naphtha mode of operation. Thefollowing results were obtained:

Temperature requirement 325° C.

Distribution of 180° C.⁻ product (in % by weight):

    ______________________________________                                               C.sub.1 --C.sub.4                                                                             16                                                            C.sub.5 - 65° C.                                                                       26                                                            65° C.-180° C.                                                                  58                                                     ______________________________________                                    

The chemical hydrogen consumption amounted to 1.5% by weight. It will beclear that the catalysts in accordance with the present invention aremore active and selective than catalysts based on known ultra-stable Yzeolites. Also the chemical hydrogen consumption is slightly reduced.

We claim:
 1. A composition of matter suitable as a catalyst (base) inhydroprocessing comprising a crystalline aluminosilicate zeolite and abinder wherein the crystalline aluminosilicate comprises a modified Yzeolite having a unit cell size below 24.35 Å, a degree of crystallinitywhich is at least retained at increasing SiO₂ /Al₂ O₃ molar ratios, awater adsorption capacity (at 25° C. and a p/p_(o) value of 0.2) ofbetween 10% and 15% by weight of modified zeolite and a pore volume ofat least 0.25 ml/g wherein between 10% and 60% of the total pore volumeis made up of pores having a diameter of at least 8 nm.
 2. Thecomposition according to claim 1, wherein between 10% and 40% of thetotal pore volume of the modified zeolite is made up of pores having adiameter of at least 8 nm.
 3. The composition according to claim 2,wherein the modified Y zeolite has a water adsorption capacity of atleast 10% by weight of modified zeolite.
 4. The composition according toclaim 3, wherein the composition comprises 5-90% by weight of modified Yzeolite and 10-95% by weight of binder.
 5. The composition according toclaim 4, wherein the composition comprises 50-85% by weight of modifiedY zeolite and 15-50% by weight of binder.
 6. The composition accordingto any one of claims 1-5, wherein the binder comprises an inorganicoxide or mixture of inorganic oxides.
 7. The composition according toany one of claims 1-5, wherein the binder comprises silica, alumina,silica-alumina, silica-zirconia or silica-boria.
 8. The compositionaccording to any one of claims 1-5, wherein the modified Y zeolite has aSiO₂ /Al₂ O₃ molar ratio of from 4 to
 25. 9. The composition accordingto claim 8, wherein the modified Y zeolite has a SiO₂ /Al₂ O₃ molarratio of from 8 to
 15. 10. The composition according to claim 6, whereinthe modified Y zeolite has a SiO₂ /Al₂ O₃ molar ratio of from 4 to 25.11. The composition according to claim 7, wherein the modified Y zeolitehas a SiO₂ /Al₂ O₃ molar ratio of from 4 to
 25. 12. The compositionaccording to claim 10 or 11, wherein the modified Y zeolite has a SiO₂/Al₂ O₃ molar ratio of from 8 to
 15. 13. A catalyst compositioncomprising a binder, a modified Y zeolite according to any one of claims1-5 and at least one hydrogenation component of a Group VI metal and/orat least one hydrogenation component of a Group VIII metal.
 14. Thecatalyst according to claim 13, wherein the binder comprises aninorganic oxide or mixture of inorganic oxides.
 15. The catalystcomposition according to claim 14, wherein the binder comprises silica,alumina, silica-alumina, silica-zirconia or silica-boria.
 16. Thecatalyst composition according to claim 13, wherein the modified Yzeolite has a SiO₂ /Al₂ O₃ molar ratio of from 4 to
 25. 17. The catalystcomposition according to claim 16, wherein the modified Y zeolite has aSiO₂ /Al₂ O₃ molar ratio of from 8 to
 15. 18. The catalyst compositionaccording to claims 16 or 17, wherein the binder comprises silica,alumina, silica-alumina, silica-zirconia or silica-boria.
 19. A catalystcomposition according to claim 13, wherein the hydrogenation componentcomprises one or more components of nickel and/or cobalt and one or morecomponents of molybdenum and/or tungsten or one or more components ofplatinum and/or palladium.
 20. The catalyst composition according toclaim 19, wherein the binder comprises an inorganic oxide or mixture ofinorganic oxides.
 21. The catalyst composition according to claim 20,wherein the binder comprises silica, alumina, silica-alumina,silica-zirconia or silica-boria.
 22. The catalyst composition accordingto claim 19, wherein the modified Y zeolite has a SiO₂ /Al₂ O₃ molarratio of from 4 to
 25. 23. The catalyst composition according to claim22, wherein the modified Y zeolite has a SiO₂ /Al₂ O₃ molar ratio offrom 8 to
 15. 24. The catalyst composition according to claims 22 or 23,wherein the binder comprises silica, alumina, silica-alumina,silica-zirconia or silica-boria.
 25. A catalyst composition according toclaim 13, wherein the hydrogenation component comprises between 0.05 and10% by weight of nickel and between 2 and 40% by weight of tungsten,calculated as metals per 100 parts by weight of total catalyst.
 26. Thecatalyst composition according to claim 25, wherein the binder comprisesan inorganic oxide or mixture of inorganic oxides.
 27. The catalystcomposition according to claim 26, wherein the binder comprises silica,alumina, silica-alumina, silica-zirconia or silica-boria.
 28. Thecatalyst composition according to claim 25, wherein the modified Yzeolite has a SiO₂ /Al₂ O₃ molar ratio of from 4 to
 25. 29. The catalystcomposition according to claim 28, wherein the modified Y zeolite has aSiO₂ /Al₂ O₃ molar ratio of from 8 to
 15. 30. The catalyst compositionaccording to claims 28 or 29, wherein the binder comprises silica,alumina, silica-alumina, silica-zirconia or silica-boria.
 31. Thecatalyst composition according to claim 13, wherein the hydrogenationcomponent(s) is (are) present in sulphided form.
 32. The catalystcomposition according to claim 19, wherein the hydrogenationcomponent(s) is (are) present in sulphided form.
 33. The catalystcomposition according to claim 25, wherein the hydrogenationcomponent(s) is (are) present in sulphided form.
 34. A composition ofmatter suitable as a catalyst (base) in hydroprocessing comprising about50-85% by weight of a crystalline aluminosilicate zeolite wherein thecrystalline aluminosilicate comprises a modified Y zeolite having a unitcell size below about 24.35 Å, a degree of crystallinity which is atleast retained at increasing SiO₂ /Al₂ O₃ molar ratios, a SiO₂ /Al₂ O₃molar ratio between about 8 to about 15, a water adsorption capacity (at25° C. and a p/p_(o) value of 0.2) of between about 10-15% by weight ofmodified zeolite and a pore volume of at least about 0.25 ml/g whereinbetween about 10 to about 40% of the total pore volume is made up ofpores having a diameter of at least about 8 nm and about 15-50% byweight of a binder comprising alumina.
 35. A catalyst compositioncomprising the composition of claim 34 and from about 0.05 to about 10%by weight of nickel and from about 2 to about 40% by weight of tungstencalculated as metals per 100 parts of total catalyst.